Treatment process for removal of metals and treating agent therefor

ABSTRACT

RADICAL IN ITS MOLECULE AND ALSO HAVE A MEMBER OR MEMBERS SELECTED FROM THE GROUP CONSISTING OF THE -N , -S-, -NH-, -N N-, and -NH-NH- radicals in the same molecule; and (c) an organic compound capable of forming a chelate compound of a metal, which compound has the -OH radical in its molecule and also a member or members selected from the group consisting of the -N and -NH2 radicals in the same molecule.   A treament process for removing metals from a gaseous phase or liquid phase metal-containing material using a solid treating agent consisting of a carrier material and a compound deposited thereon, such compound being selected from (a) an organic compound capable of forming a mercaptide compound of a metal, which compound has the -SH radical or an alkali salt thereof in its molecule and may also have a member or members selected from the group consisting of the -N , -S-, -NH-, -N N-and -NH-NHradicals in the same molecule; (b) an organic compound capable of forming a mercaptide compound of a metal, which compound has the

United States Patent 191 Yokota et al.

[ TREATMENT PROCESS FOR REMOVAL OF METALS AND TREATING AGENT THEREFOR [75] Inventors: Norlyukl Yokota, Ashiya; Shingo Tokuda, Nishinomiya; Yoshlro lto, Amagasaki; lllroshl Takatoml, Osaka, all of Japan [73] Assignee: Osaka Soda Co., Ltd., Osaka, Japan [22] Filed: Jan. 5, 1971 [21] Appl. No.: 104,160

[30] Foreign Application Priority Data Feb. 5, 1970 Japan ..45/l0146 Feb. 26, 1970 Japan ....45/17353 Feb. 26, 1970 Japan .....45/l7354 April 13,1970 Japan ..4S/31412 [52] US. Cl 210/36, 55/72, 55/73, 55/74, 210/38 [51] Int. Cl B01d 15/00 [58] Field of Search 55/72, 74, 75; 210/24, 36, 38; 260/429, 429.5

[56] References Cited UNITED STATES PATENTS 3,196,107 7/1965 Tomic 210/38 3,310,530 .3/1967 White 210/38 X 3,284,351 11/1966 Dajani et al. 210/38 X 2,645,621 7/1953 D'Alio 210/36 X 3,111,503 ll/l963 O'Connor et al. 260/429 J 3,408,291 10/1968 Thomas et al. 210/38 X 2,954,276 9/1960 Hazen 210/38 X 3,420,709 1/1969 Barrett, Jr. et a]. 210/36 X [111 3,755,161 51 Aug. 28, 1973 Primary ExaminerSamih N. Zaharna Attorney-Sherman & Shalloway [57] ABSTRACT A treament process for removing metals from a gaseous phase or liquid phase metal-containing material using a. solid treating agent consisting of a carrier material and a compound deposited thereon, such compound being selected from (a) an organic compound capable of forming a mercaptide compound of a metal, which compound has the Sl-l radical or an alkali salt thereof in its molecule and may also have a member or members selected from the group consisting of the N=, S, Nl-l-, --N=Nand NH-NH- radicals in the same molecule; (b) an organic compound capable of forming a mercaptide compound of a metal, which compound has the 7 Claims, No Drawings TREATMENT PROCESS FOR REMOVAL OF METALS AND TREATING AGENT THEREFOR This invention relates to an improved treatment process by which residual metals contained in gaseous phase (a terminology inclusive of vapor phase) or liquid phase (a terminology inclusive of the liquid phase in a slurry state) materials to be treated can be removed with an excellent removal capacity, down to a low concentration such as can be indicated in ppb units (1 ppb 1/1000 ppm), using a readily manufactured and readily available treating agent, while maintaining the foregoing capacity of the treating agent for a prolonged period of time and, moreover, at an especial advantage from the standpoint of the equipment and operations involved.

More specifically, the invention relates to a treatment process for removing metals and a treating agent to be used therein, such process being characterized in that the gaseous or liquid phase metal-containing material to be treated is contacted with in solid treating agent which consists of a carrier material supporting by adsorption thereto a compound selected from the group consisting of g a. an organic compound capable of forming a mercaptide compound of a metal, which compound has the Sl-l radical or an alkali salt thereof in the molecule and may also have a member or members selected from the group consisting of -N=, S-, -NH--, N=N- and NH-NH radicals in the same molecule;

b. an organic compound capable of. forming a mercaptide compound of a metal, which compound has the radical in the molecule and also has a member or members selected from the group consisting of the N=, S-, NH, N=N- and NH-NH radicals in the same molecule; and

c. an organic compound which can form a chelate compound of a metal, which compound has the -OH radical in the molecule and also has a member or members selected from the group consisting of the -N= and -NI-l radicals in the same molecule.

l-leretofore, the following metal-containing waste gases, waste liquids and the like are known: concentrated aqueous caustic alkali solution obtained from the electrolysis of alkali salts by the mercury cell; hydrogen gas and synthetic hydrochloric acid synthesized from said hydrogen gas and chlorine gas; various other waste water and waste gases formed during the electrolysis of alkali salts by the mercury cell; various waste liquids and waste gases which are produced during the smelting of zinc, mercury, copper and other metals; waste water of the plating industry; waste liquors containing catalysts or decomposed products thereof, which have been used in the polymerization reaction and other catalytic reactions; various waste liquors of the synthetic chemical industry which use metal compounds; and other metal-containing and especially heavy metal-containing waste gases, waste liquids and the like, which are produced in a broad range of inorganic and organic industries and the mining industry.

Lately, the desire is especially great that these metals be removed from these generally harmful metalcontaining waste gases and waste liquids to such a low content as to be substantially tolerable for preventing the environmental pollution, inclusive of the instances in which the conjoint purpose is to recover the metals contained.

The usual method which is employed for removing the metals from the metal-containing materials to be treated is either that in which themetal is precipitated or flocculated by adding a precipitating agent or a flocculating agent and thereafter isolating and collecting the metal, or that in which the metal is absorbed and isolated by using an adsorbent such as active carbon.

However, in the case of the former method it was exceedingly difficult to separate the supernatant liquid and the metal-containing precipitate or flocculate from the large quantity of the waste liquid being treated. Further, there was the necessity for the use of a great quantity of the treating agent and the need for a large scale precipitating apparatus or precision filtration apparatus for fully separating and removing the fine'metal-containing solids portion. On the other hand, in the case of the latter method, it was very difficult to reduce the concentration of the residual metal in the liquid to as low a content as desired.

Further as the method of removing the metals from the gaseous phase metal-containing materials to be treated, and particularly the removal of the vapor phase metals, inter alia mercury contained in the gas, the method known heretofore was either that of cooling the gas to a low temperature at normal pressure or superatmospheric pressure of 3-5 kg/cm and condensing the mercury vapor and separating same, or that in which the mercury was absorbed by passing the gas through a layer packed with active carbon or a molecular sieve.

However, the former of these methods requires a large-scale cooling equipment for cooling the gas, while the latter method has the drawback that in the case of active carbon and molecular sieve the amount of mercury absorbed in the gas is small, with the consequence that they are relatively poor in efficiency as adsorbents for they are required to be used in large quantities.

Again, as a chemical method of removing metals from metal-containing materials in the gaseous phase, there is a method of removing mercury from hydrogen gas as a mercuric chloride by treating with a hypochlorite. Further, a method of treatment by means of a sulfuric acid-added potassium permanganate solution is also practiced, but there is the drawback that the adjustment during the operation is difficult and that recontamination of the gas by means of the excess chlorine takes place.

In addition, as a method of treatment with ozone, there is a method in which the gas containing the mercury is treated with ozone and separation is carried out with an electrostatic separator or mechanical filtration, but difficulty is involved in the separation or filtration operation.

While several instances of possible methods have been described hereinbefore, the removal of metals from the gaseous or liquid phase metal-containing materials being treated, inclusive of the instances where the conjoint purpose is to recover the metals, not only involves considerable difficulties but also possesses drawbacks which need solution. There is particularly the limitation that a costly method from the standpoint of the treating agent, apparatus and operations cannot be utilized for the solution of the foregoing difficulties and drawbacks, since in the case of these waste liquids and waste gases the amount to be treated is usually very great, and hence the solution of the problem is made very great, and hence the solution of the problem is made much more difficult. This is the present state of affairs.

As a result of our researches with a view to overcoming the foregoing difficulties and drawbacks and providing a method which can be carried out advantageously without being subjected to the aforesaid limitation, we found that by using a solid treating agent to which has been adsorbed and deposited a certain or ganic compound which is capable of forming a mercaptide compound or an N,O- co-ordinate chelate compound of a heavy metal, metals could be removed with a remarkably excellent metal capturing capacity from the metal-containing material being treated regardless of whether it is in a gaseous or liquid phase and moreover with this removal capacity being maintained stably over a prolonged period of time. On the basis of this finding, we were able to succeed in developing a treatment method which demonstrates greatly improved results.

Further,-it was found that the coordinative conditions involving (1) the use as the adsorptive carrier material a carbonaceous material or other adsorptive carrier materials, which have been used heretofore independently for these treatments, and (2) the deposition thereon by adsorption thereto of the hereinbefore described organic compound were indispensable for achieving the objectives of the invention, and that a metal captivating and removal capacity of high degree wholly unexpected by the use of the organic compound and carrier separately was demonstrated.

It is therefore an object of the present invention to provide an improved treatment process by which metals contained in a gaseous or liquid phase metalcontaining material being treated can be captured and removed with remarkably excellent removal capacity, using a readily manufactured and readily available inexpensive treating agent. Another object is to provide a method of removing the aforesaid metals advantageously with an exceedingly simple apparatus and operation with no limitation from the cost standpoint while maintaining the metal removal capacity of the afore said treating agent over a prolonged period of time. A further object is to provide an inexpensive treating agent of high performance, which is suitable foruse in the hereinbefore described treatment.

Other objects and advantages of the present invention will become apparent from the following descriptron.

In the process of the invention a solid treating agent consisting of an organic compound capable of forming a mercaptide compound or an N,O- co-ordinate chelate compound of a metal, which is supported by a carrier material by adsorption thereto is used.

The foregoing organic compound is selected from the following groups (a), (b) and (c);

a. an organic compound capable of forming a mercaptide compound of a metal, which compound has the SH radical or an alkali salt thereof in the molecule and may also have a member selected from the group consisting of the S, NH-, N=N and NHNH-- radicals in the same molecule;

b. an organic compound capable of forming a mercaptide compound of a metal, which compound has the radical in the molecule and also has a member selected from the group consisting of the N=, S, NH, N=H- and NH-NH- radicals in the same molecule; and

c. an organic compound capable of forming an N,O coordinate chelate compound of a metal, which compound has the OH radical in the molecule and also has a member selected from the group consisting of the 13 N= and NH, radicals in the same molecule.

As examples of the these compounds, those of group (a), above include the following groups (1) (4) l. Mercaptide compounds of the formula R-S-M wherein R is an aromatic group or a group having a terminal CH= or CH, radical, and M is hydrogen or an alkali metal.

2. Thiazole compounds of the formula wherein R is an aromatic group and M is hydrogen or an alkali metal.

3. Di-alkyldithiocarbamic acid of the formula N=c i-sM wherein R is a C, C alkyl radical, methyl, ethyl, n butyl, etc., and M is hydrogen or an alkali metal. (4) Xanthates of the formula R-O-C-S-M wherein R is butyl or isopropyl and M is hydrogen or an alkali metal.

Specific examples of the compounds or group (a) include the following organic compounds which can form a mercaptide compound of a metal.

2-Aminoethanethiol (H,NCH,CH,SH)

butyl-mercaptan (C,H,SH)

Cyclohexylamine salt of Z-mercaptobenzothiazole CH -CH:

Q Di-alkyldithiocarbamic acid (alkali metal salt) alkyl radical like as methyl, ethyl and n-butyl, M; alkali metal b 2.3-dimercapto-l-propanol S II JJH-CHzOH H SH Q Glutathione is Bismuthiol II HOC-CH-CH CHzCONHCHCO-NHCHz-COOH I I I Q NH; CH SH I Q 2-mercaptobenzothiazole a S 5 KS S c u p-dimethylaminobenzylidenezhodamine,

G-SH

s N is; and its alkali metal salts. 10 5 ll) 2-mcrcaptocthanol (ll0CII --CH SH) ll Di-fl-naphthylthiocarbazono il Pipccolin pipecolyl dithio carbamate 6; dl-mcrcaptosuc(:inic acid I il-mp A IISCIICOOII I l CIIzCOOH 5:0

S L-N A l H CHaCaHqN --SH-NC5H@CH3 l Piperidine pentamethylene dithio carbamate 7 1 g fi is Dithizone c 2 N-C-SH-HN 0H, H

GHQ-CH: cal-0H1 S a Tlliozlcctic acid (CHgCOSH) k Tllioglycolic acid (HSOH COOH) o and its alkali k! Q 2-mercaptobenzimidaz0le (O-phenylene thiourea) H H Nncocmsn N N @3 C-SH c=s Q Thiophenol N L S H Is 2dliercaptoimidaaolille letllyleuethiourea) H C-NH H C-NH I CSH \C=S is and its alkall metal salts. V Ere-N H1C-NH h Isopropyl xanthlc acid Thiocarbanilide I H c s K II "Q- l CHO-C-SH H c=s 3C is and its alkali metal salts. Q' E; J

Examples of the compounds of group (b), above, in- Di-orthotolylthioufa clude the following f CH3 l. Thiocarbazones of the formula Q 1% R-NH-NH /C: S H RN=N CH3 J b Trimethylthiourea wherein R is an aromatic group. CH:

2. Thioureas of the formula N Ca \C=S RNH CH;N C=S H RNH On the other hand, specific examples of the compounds of group (c) include the following organic compounds which can form an N,O co-ordinate chelate wherein R and R are each an aromatic group or a C compound of a metal;

C alkyl radical.

3. Z-Mercaptobenzimidazole. A' fln-gma 4. Z-Mercaptoimidazoline.

Specific examples of the compounds of group (b) include the following organic compounds which can form NH a mercaptide compound of a metal.

Oxinc 2-1nctl1yl oxine, i.e., 8 hydroxyquinaldinc N CHL.

While the hereinabove illustrated organic compounds, which are useable in the present invention, include both those which are water-soluble as well as water-insoluble, these compounds can be dissolved in such solvents which are suitable for the several compounds and be deposited on a carrier material by adsorption thereto.

As these solvents, mention can be made of such, for example, as water, aqueous alkaline solutions containing an inorganic alkaline substance such as alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates and ammonia; methanol, ethanol, propanol, butanol and other C C aliphatic alcohols; the halogenated lower hydrocarbons such as dichloromethane, trichloromethane and trichloroethylene; dilower alkyl carbonyls such as dimethyl carbonyl; carbon tetrachloride; chloroform; and acetone.

These solvents are imposed no restrictions and can be used so long as they do not react with the foregoing organic compounds (i.e. are inert thereto) and can dissolve same. Of these solvents, preferred are those which can be readily removed after the aforesaid organic compounds have been deposited on the carrier material by adsorption thereto by such means as waterwashing, washing in a dilute aqueous acid solution, evaporation, vacuum drying and air drying.

Needless to say, the use of a solvent can be dispensed with in the case where the organic compound used is one which is normally liquid.

In effecting the deposition on the carrier material by adsorption thereto of the hereinbefore described organic compound or a solvent solution thereof, any method by which the organic compound or solution thereof is brought fully into contact with the carrier material can be employed. For example, the carrier material can be submitted to an immersion treatment in these solutions, or the solutions can be flowed down through a column packed with the carrier material, or various other methods of contacting the liquid phase with the solid phase can be utilized. This operation of effecting the deposition of the organic compound on the carrier material by adsorption of the former to the latter is usually carried out at room temperature but, if desired, the operation can be carried out under heated conditions of 30 70C.

After the deposition treatment, the resulting solid treating agent can be directly used but, if desired, it may be used after having been submitted to waterwashing, washing in a dilute aqueous acid solution, evaporation, vacuum drying, air drying and other treatments to remove the solvent contained therein.

As the carrier material constituting the substrate of the solid treating agent to be used in the present invention, those obtained from natural or artificial sources can be widely used, but those selected from the group consisting of the carbon carriers such as active carbon and bone black, silica gel, zeolite and silica-alumina gel containing at least 50 percent by weight of silica gel demonstrate exceedingly superb improved results and thus are recommended. If desired, the organic high molecular weight adsorbents and molecular sieves can be used as the carrier material, but these are not desirable because of their high cost. Further, such carriers as alumina, magnesia and the naturally obtained quartz sand can also be used, but results obtained are inferior to those obtained in the case of the use of the hereinabove recommended carrier materials.

The size of the carrier particles can be varied over a broad range and those on the order '00 180 mesh, and preferably 6 of 2 mesh, may usually be used. Again, the amount in which the aforesaid organic compound is deposited on the carrier material by adsorption thereto can also be varied over a broad range, and an amount on the order of l 30 percent by weight, and preferably 2 20 percent by weight, based on the carrier material, may usually be used. The particles size of the carrier material and the amount of the organic compound to be deposited thereon by adsorption thereto, as indicated above, can be suitably modified in accordance with the class of the carrier material, the class of the organic compound, the class of the material to be treated, the method used in effecting the contact of the material to be treated and the solid treating agent and the treatment speed.

No special restriction is imposed as to the method to be used in effecting the contact between the solid treating agent, such as hereinabove described, and the gaseous or liquid phase metal-containing material to be treated in accordance with the invention process. All of the liquid-solid phase or gaseous-solid phase contacting methods which are capable of fully contacting the treating agent with the material being treated can be utilized. While the batch method of contact can be employed, preferred is a continuous contact method such, for example, as the column method.

For example, the material being treated can be caused to flow downwardly through a column packed with the solid treating agent or conversely be caused to flow upwardly through the column; or while forming a fluidized bed of the solid treating agent the gaseous phase material being treated can be passed through such bed; or if the material being treated is of liquid phase, it can be sprayed. While the contact treatment can be carried out in a single stage, it also can be carried out in a multistage fashion by providing a plurality of contact zones through which the material being treated is passed. While there is no particular restriction imposed as to the temperature at which the treating agent and the material being treated are contacted, a range of 5 35C. is frequently employed.

The contact time or speed of the solid treating agent with the gaseous or liquid phase material being treated can be readily varied by those skilled in the art in accordance with the class of the organic compound, the class and particle size of the carrier material and amount of the organic compound supported, the class of the material being treated and the method of contacting the solid treating agent with the material being treated. In general, the optimum conditions can be readily determined experimentally over a range of SV (space velocity) =0.2 20 l/hr in the case the material being treated is of liquid phase and over a broad range "on the order of SV 50001/hr in the case the material being treated is of gaseous phase, in accordance with the hereinbefore indicated various factors.

As the metals to be contained in the gaseous or liquid phase metal-containing material to be treated by the invention process, those metals selected from the group consisting of Hg, Au, Bi, Cd, Co, Cr, Cu, Ni, Pb, Zn, Ag, Mn, Fe, Mo, Ti, Mg and Al can be mentioned. The invention process can be employed with special advantage in the treatment of a gaseous or liquid phase material containing at least one of the foregoing metals.

The hereinbefore described organic compound is preferably chosen in accordance with the class of the metal contained in the material to be treated. For example, thionalide, Z-mercaptobenzothiazole and pdimethylaminobenzilidene-rhodanine are preferably used in the case of Hg, Cu, Au, Ag, Cd and Pb; oxine and Z-mercaptobenzothiazole, in the case of Bi, Co, Ni and Zn; and oxine and 8-hydroxyquinaldine, in the case of Mn, Cr, Fe, Mo, Ti and Mg. When the material to be treated is one containing a plurality of metals, a pinrality of organic compounds can be used.

In the case where the material to be treated is one of liquid phase, it is possible according to the invention process to pretreat the material with an anion exchange resin and thereafter contact the so pretreated metalcontaining material with the aforesaid solid treating agent. in general, when the content of metal is very great and the recovery of the metal is also intended, a pretreatment of this kind is desirable. Since the recovery of the metal from the anion exchange resin is a relatively simple matter, the metal contained in the metalcontaining material being treated can be recovered with this pretreatment, after which the reduced amount of metal contained in the residual liquid can be contacted with the solid treating agent to effect its removal by fixation to the treating agent.

As such an anion exchange resin, mention can be made of those having as the exchange group such, for example, as -N-(CH X,

o Hrorr N(R) -NH(R), NH and -N(CH wherein X is an anion such as Cl", OH, etc., and R is an alkyl radical such as CH C I-l etc.

The pretreatment operation is carried out in the following manner. The material being treated is passed successively through a column packed with the hereinbefore described anion exchange resin. Alternatively, the anion exchange resin is introduced into the treatment tank and the adsorption is carried out with stirring, after which the resin is separated from the treated liquid.

plied to the removal of Hg from the concentrated aqueous caustic alkali solutions obtained in the mercury cell method of electrolysis of alkali salts; the removal of Hg of the hydrogen gas evolved during the aforesaid electrolysis; the removal of Hg contained in the synthetic hydrochloric acid synthesized from hydrogen gas and chlorine gas; in addition, the removal of Hg from the various waste gases and water that are produced during the mercury method of electrolysis of alkali salts; the removal of Hg, Cd, Mn, Cr, Cu, Fe, etc., from the various waste gases and water which are produced during the smelting of various metals; the removal of Cr and Cu from the waste water of the plating industry; the removal of Hg, Cd, Mn, Cr, Cu, Fe, etc., from the waste liquids containing catalysts or decomposition products thereof, as well as from the waste gases and water produced in the synthetic chemical industry; and the removal of metals contained in a wide range of other gaseous and liquid phase materials.

The following examples and control experiments are given to illustrate several modes of practicing the present invention.

EXAMPLES l 2 AND CONTROL 1 Three hundred ml'of carbon tetrachloride in which were dissolved 150 mg of dithizone were flowed down through a glass tube of 8 mm inside diameter packed with 5 grams of active carbon thereby causing the adsorption to and deposition on the active carbon layer of dithizone. The amount of dithizone absorbed and deposited was about 150 mg. This dithizone-supporting carrier was left standing for 24 hours to cause the carbon tetrachloride to volatilize. This was followed by flowing a saline prepared from mercuric chloride and sodium chloride (mercury content 1.4 mg per liter) down through the tube at the rate of cc per hour. This test was repeated ten times. In every case the mercury concentration of the effluent became less than 5 pp Further, about 5 grams of the dithizone-supporting carrier prepared as in Example 1 were added to 200 ml of saline containing 1.4 mg/l of mercury, the contact being carried out for one hour with gentle stirring (Example 2), with the result that the mercury concentration of the aqueous solution became less than 5 ppb.

A control, the experiment was carried out exactly as in Example 1 except that the adsorption to and deposition on the active carbon of the dithizone was not carried out and 5 grams of active carbon were used (Control l). The test was repeated 10 times and in every instance the mercury concentration of the effluent was above 420 ppb.

The results obtained in the foregoing experiments are shown in Table l.

TXBZ"E"I""" V s Treating agent 0 d Metal qoncegigration rganic compoun p.p.

. Carrier Amount Metal Before After adsorbed Weight to be treattreat- Experlment No. Name (Wt. percent) Name (g.) removed ment ment Example 1 Dithizone. 3 Active carbon... 5 Hg 1, 400 5 Example 2 (batch method) ..do 3 do 5 Hg 1, 400 5 Control 1 ..d0 5 Hg 1, 400 420 The invention process can be applied as a treatment method for removing metals from the gaseous or liquid phase metal-containing materials extending over a wide range from those which are acid to those which are alkaline. For example, the invention process can be ap- As is apparent from the results given in the Table 1, above, it can be seen that totally unexpected results were achieved in accordance with the invention process as compared with the case where the adsorbent carrier was used alone.

and Control I except that Z-mercaptobenzothiazole and silica gel were used as the organic compound and carbon thereby effecting the thorough adsorption to and deposition on the active carbon layer of the thionalide, followed by removal of the solvent by blowing in air. A solution containing 5.6 mg per liter of mercury carrier, respectively, and the carrier weight, amount of was flowed down through thionalidesuppomng the organic compound deposited thereon by adsorption and the Hg concentration of the material treated were varied. The results obtained are shown in Table 2.

carrier at the rate of 130 ml per hour, whereupon the mercury concentration of the effluent became less than 50 ppb.

TABLE 2 Metal concentration Organic compound (ppb.)

Carrier Amount Metal Before After deposited Weight to be treattreat. Experiment N Na e (wt. percent) Name (g.) removed ment men 2- erca tobenzothiazole Hg 13,900 5 gbg t i l f l0 Hg 13,900 13, 000

The results presented in Table 2 show, as in Table l,

the totally unexpected results that can be obtained by the invention process.

EXAMPLE 4 EXAMPLES 5 28 The experiments were carried as in Example 4, using as the method of contact either the column method or the batch method described in Example 2 and various One hundred mg of thionalide in solution in 100 ml bi i f h organic compound and rri r,

of dichloroethane were flow down through a glass tube of 8 mm inside diameter packed with 5 grams of active TABLE 3 Solid treating agent Organic compound used Carrier Amount de- Experiment, posited (wt. Weight No. Name percent) Solvent used Name (g) Example 5-..- Z-mereaptobenzothiazole 10 CHgClg Aetive carbon Example 6-.-- Thionalide 2.. (1

Example 20... 2,3-dimercapto-l-propanol Example 21... Z-mercaptoethanol Example 22... Na salt of 2-mcrcaptobenzothlazole... Example 23... 'Ihionallde Example 24... Bismuthlol Il Z-mercaptobenzothiazo plus anthran 0 acid T so p-Dimethylaminobenzylidene rhodanine plus Z-mercapto- Acetone ..d0.................

benzothiazole. Example 27... Oxine plus pipeeolinc pipecolyl dithlocarbamatc. lo ..do ..do Example 28-.. S-hydaoxy quinaldine plus p-dimethylamino-benzylidene 5 ..do ..d0

r o amne.

Time contacted with liquid material (batch method) or space Metal Material treated Metal concentration being treated .p.b.)

velocity (column method), to be Before After Expenment No. l./hr. removed Property treatment treatment Example 5 6 5 l151g 2 50] 5,600 5 t g q. sol 5,600 50 hxample 6 1o iame as above.. 2,500 10 E H g so 5,600 5 ample 7 "{ge Same as above. 300

r q. s 500 70 Example 8 7 5 {Mn Same as above. 700 50 Examplet) 7.0 Hg l3.900 5 Example 10. 7.8 Cd 200 Example 11. 8.0 Hg 5,600 5 Example 12. 0.0 Hg 9,800 5 Example 13. 10 5 Hg 10,200 5 Example 14. Hg 25,000 250 Example 15 Contact time 2.5 hours. Hg 8, 200 7 Same as abov 600 Ag. so] 5,500 0 Same as above. 500

Aq. sol 5,600 8 Same as above l, 200 54 Material treated Time contacted with liquid let:\l concentration material being treated (p.p.b,) (batch method) or space Metal velocity (column method). to be Before After Experiment No. l./ln'. removed Property treatment treatment Example 18 2.1 Example 10.... 1.1.. 1,800 X Example '20 1.0.. 2, .200 12 Example 21 1.0.. 2.100

Hg 8,200 8 Example 22 2.0 600 50 i s ""1; l'E ameas a ove.. 1 Example 23 g 0 75 1,600 100 750 1,200 55 0,800 20 900 1,500 3,500 25 700 40 7,700 7 2,400 35 420 15 .\111 Sq. s ...5 1,% 6. Cr ame asa ove-. 1 xample 27 0 Fe "mdo U 900 25 Mo Aq. sol 950 Ti Same as above. 1,300 Example 28 6 5 Mg 75 30 Ag .....do 1.200 30 EXAMPLES 29 55 AND CONTROL 3 latter, mercury-containing aqueous caustic alkali solu- Experiments were carried out with the mercury- 25 tions were used. The results obtained are shown in containing an acid property and those having an alkaline property. As the former, mercury-containing concentrated aqueous hydrochloric acid solutions were used while, as the materials to be treated being those having pound was not deposited on the active carbon.

Table 4. Also shown in Table 4 are the results obtained as Control 3 wherein the experiment was carried out exactly as in Example 53 except that an organic com- TABLE 4 Solid treating agent Organic compound used Gamer Amount Experiment deposited eight No. Name (wt. percent) Solvent used Name (L..)

Example 20. Na salt of 2-mercaptobenzothiazole 10 00 Example 30. 40 Example 31... 2" Example 32. Example 33.-. 10 Example 34. p-Dimethylaminobenzylidene rhodanine. 10 Example 35... Di-fi-naphthyl thiocarbazone 10 Example 36... 2-mercaptobenzothiazole 10 Example 37... Bismuthiol II Example 38... Thiophenol 10 Example 30... Iiperidine pcntamethylene thiocarbamate. 10 Example 40. iZ-meroaptoimidazoline 10 Example 41... Sodium dicthyldithiocarbamate About 5.0.. 30 Example 42... 2-niemaptolmnzothiazolc About 3.0.. Exnmplwl-i... p-l)imethylmninohcnzylldcim rhodanine About 1.5.. 30 Example 44. Sodium (llothyldithiocarbamatc About 5.0.. ACIIVO carbon-4 150 Example 45. iZ-morcnptobenzothlazolo 10 40 Example 40. L-cystcinc 6.0. 50 Example 47.. Sodium salt of .l-mercaptobenzothiazole About 5 0 40 Example 48. (llutathionc (reduced type) About 3 0. Carbon 50 Example ll). L-cystcine About 2.0.. Vi Molecular Example 50. llismuthiol n .5 e Actlve a 40 Example 51. Sodium salt 01' tliiophenol 1.0 3cm"? Carbon 50 Example 52. 2-mercaptobenzothiazole About 1.5.. Acetone... 1 40 Example 53... Thioglycolic acid About 1.0.. Vi SIP! AQUVE 93143011 40 Example 54... Di-B-naphthylca,rbazone About 2.0. Chloroform. 40 Example 55. Thionalide About 2.5 Diehloromethaue F d. act carbon 50 c m 3 Active carbon 4 Material treated Metal concentration (Imp- Metal to Time contacted with liquid material being treated (batch method) be re- Before hrs. Experiment No. or space velocity (column method) l./hr. moved Property treatment later Example 29 Contact time 2 hours Hg Cone. HCl 2, 500 7 Example 30- 11.0 Hg 1, 700 4 Example 31 Contact time 2 hours. Hg 700 6 Example 32 Contact time 2.5 hours. Hg 1, 700 30 Example 33- ....do..-- Hg 1, 700 28 Example 34 Contact ti on Hg 1, 700 5 Example 35. Contact time 2.5 hour Hg 1, 700 30 Example 36. Contact time 2.0 hour Hg 1, 300 12 Example 37. Contact time 3.0 hours. Hg 1.300 24 Solid treating agent Organic compound used Carrier Amount Experiment d it d \l eight No. Name (wt. percent) Solvent used Name (9,.)

Example 38 Contact time 2.0 hours Hg HCl 35% 1, 300 30 Example 30 Contact time 2.5 hours Hg P101357. 1, 300 15 Example 40 ..do Hg 11Cl35% 1,300 25 Example 41 ..do Hg 1,700 30 Example 42 1 1 .do 1, 700 Exam plo 43 .(lo... 1, 300 8 Example 44 Contact time 3 hour. 150 30 Examplev 45 0.7 250 Example 46 1.5.. 120 10 Example 47 2.0. 120 10 Example 48 0.8. 200 30 Examplo40 1.2.. 100 15 Example 50 05.- 100 15 Example 51 0 4. 130 30 Example 52. 200 27 Example 53. 150 25 Example 54- 100 30 Example 55. 130 30 Control 3 150 120 assin h dro en EXAMPLES 56 67 AND CONTROL 4 P 8 Y 8 835 mammg 9 1 mg P P meter of mercury through the tube at a space velocity Sixty grams of 2-rnercaptobenzothiazole were dis- Of 5 H a r om t mp r p n the mersolved in 1.2 liters of a caustic soda solution of 3% conry Content of the hydrogen gas after passage throu h centration, after which the resulting solution was the was 0-00 g/ 6 hours later, 0-002 'flg/ m flowed down through 300 grams of active carbon of 6 hours later and 0.002 mg/m 90 hours later.

20 mesh to effect the full adsorption of the former to xpe iments were carried out as in the hereinabove the latter. The amount adsorbed was about 18 percent described Example 56, varying the organic compound by weight based on the active carbon. and the class of the carrier. The results obtained are After water-washing and air drying the Z-mercapshown in Table 5, below, along with the results of Extobenzothiazole-adsorbed active carbon particles, they 30 ample 56. Also presented are the results of Control 4, were packed in an acrylic resin tube of 60 mm inside which was also carried out as in Example 56 but withdiameter and about 25 cm high. This was followed by out deposition of an organic compound on the carrier.

TABLE 5 Solid treating agent Organic compound used Carrier Amount Experiment deposited Weight No. Name (wt. percent) Solvent used Name (g.)

Example 56 2-mm'captobenzothiazole l8 3% aq. NaOH sol Active carbon 300 Control 4.... d 300 Example 57 p 25 Example 58. 20 Exam pin 50. 25 Example 00 2morcaptolmnzothiazole. Example 01-. do 75 Example 02.. ....(lo 1 5.0 ..do 20 Example 63 lipecolino pipacolyl dithiocarbnmato 3.0... Acctone.. Zoolite 30 Example 64... 2-morrgzaptobenzothiazolo plus pipecoline pipecolyl (lithio- 6.0 ..do Active carbon 25 car amato. Example 05... imorcaptobenzothiazolo 10.0 3% aq. NaOH sol 25 Example 'Ihioplienol 1.0 Ethanol 25 Example 67... Sodium salt 01 2-mercaptobenzothiazole 5.0 Water ..do 10 Metal concentration gdmfi) Material treated After treatment Space Metal Before velocity to be treatment 6 hrs. 90 hrs.

Experiment No. (l./hr.) removed later later Example 56 2,500 Hg 9,100 1- 2 Control 4 2,500 Hg 9,100 2, 700 9,100 Example 57 1,100 Hg 14,100 2 4 Example 58 4,300 Hg 9,000 2 7 Example 59 1,800 Hg 10,600 1 3 Example 60 1,700 Hg 11,500 2 8 Example 01 1,100 Hg 8,400 2 10 Example 62 2,000 Hg 1,500 2 7 Example 63 1,400 Hg 8,200 3 0 Example 64 2,100 Hg 11,100 3 9 Example 65 850 Hg 2,100 l Example 60 1,000 Hg 8,600 4 13 Example 67 2,100 Hg 9,200 3 7 l7 EXAMPLE68 An acrylic resin tube of 80 mm inside diameter was packed with 3 grams of an anion exchange resin. The height of the layer was about 1000 mm. When waste water containing 13,700 ppb of mercury was flowed down through this tube at a space velocity of 12 l/hr, the mercury concentration 20 hours later was 150 ppb and 120 hours later was 560 ppb.

Further when this treated liquid was flowed down through an acrylic resin tube of 120mm inside'diameter, which had been packed in advance with a fixed layer (layer height of 1050 mm) of a treating agent consisting of 8.2 kg'of l 30'mesh bone black on whichhad been deposited by adsorption thereto 0.7kg of Z-mercaptobenzothiazole, the mercury concentration 20 hours later was 2'ppb and l20=hours later was ppb.

EXAMPLE 69 A polyvinyl chloride column havingan insidediameter of 280 mm was packed'with 52 kg of an anion exchange resin. The layer heightwasabout 1200mm. When waste water containing 9400 ppb of mercury was "1s ppb of mercury was carried out under substantially identical conditions as hereinabove, the mercury concentration in the waste water after hours of treatment with the anion exchange resin was 340 ppb. When this waste water was further treated with the fixed layer of the treating agent, the mercury concentration was 3 ppb. On the other hand, the mercury concentration after 170 hours was 900 ppb after treatment with the anion exchange resinand 5 ppb after treatment with the treating agent. Further, when waste water containing 8000 10,000 ppb of mercury was treated under identical conditions while repeatedly carrying out the desorption and recovery of mercury of the anion exchange resin"anditsregeneration step, the number of days duration that the treating agent could stand use, i.e. the number of days until the mercury concentration in the-waste water subsequent to the treatment with the fixed layer of the treating agent reaches 10 ppb, was

v200 days.

EXAMPLES 7o 73 Experiments were carried out as in Example 68, varying the carrier, the organic compound deposited thereon and the material treated. The results obtained flowed down through this column ata space velocity of' 25 we howgirl T ble 6'.

TABLE 6 Solid treating agent Pretreatment Organic compound used Carrier Amount used of anionic Amount exchange I deposited Weight Experiment No. resin (g.) Name (wt. percent) Solvent used Name (g.)

Example 70 63 Thionalide 1. 6 Acetone Silica gel 120 Example 71 1,700 Pipecoline pipecolyl dithioearbamate. 5.0 3% aq. NaOH sol... Active carbon"... 1, 000 Example 72 4, 000 Z-mercapyobenzothiazole 5. 0 Same as above ..do 1, 600 Example 73 63 p-Dimethylaminobenzylldene rhodanine 4.0 Acetone do.

Metal concentration (p.p.b.)

Alter passage through treating agent Contact time with material treated or space velocity Material treated After passage column (120 through resin hrs. later) Metal column or or after Experiment Treatmg ent to be Before after contact contact with No. Resin column (L/hr.) column (1. hr.) removed Property 7 treatment with resin treating agent Example 70... 3.0 1.9 Hg Aq. waste Water. 7,000 240 5 Example 71... Contact time about 3 hours. Contact time about 2.5 Hg .....do ,600 900 4 ours. Example 72. Contact time about 4 hours. Contact time about 2 hours. Hg Aq. slurry.. 5,200 500 7 Example 73.. 2.0 2.0 Hg Aq. 301..... 10,200 350 4 l0 l/hr, the mercury concentration 25 hours later was 120 ppb and 170 hours later was 860 ppb. Further, when this treated liquid was flowed down through a polyvinyl chloride column having an inside diameter of 600 mm, which had been packed in advance with a fixed layer (packing height 950 mm) of a treating agent consisting of 125 kg of 10 40 mesh active carbon on which had been deposited by adsorption thereto 22 kg of 2- mercaptobenzothiazole, the mercury concentration 25 hours later was 2 ppb and 170 hours later was 3 ppb.

Now, when the adsorbed mercury was desorbed and recovered and the anion exchange resin was regenerated but the fixed layer of the treating agent was left intact and the treatment of waste water containing 8200 EXAMPLES 74 78 AND CONTROL 5 Fifty grams of thionalide in solution in ml of dichloromethane were flowed down through a glass column'of 8 mm inside diameter packed with 15 grams of a carrier material to cause the adsorption to and deposition on the carrier of the thionalide, followed by air drying and waterwashing the carrier. A solution containing 5600 ppb of mercury and 1500 ppb of copper was flowed down through the foregoing packed column, after which the metal concentration was measured with the results shown in Table 7. As can be seen from the results given in this table, better results are had by the use of carbon, silica gel and zeolite, as compared with the other readily available carrier materials such as alumina and magnesia.

TABLE 7 Metal concentration (p.p.b.)

Before treatmeut After treatment Experiment Organic No. Carrier compound Hg Cu Ilg Cu Example 74..." Active carbon..." 'Ihionalide 5,600 1,500 50 10 Example 75 Silica gel do 5, 600 1, 500 65 15 Example 76 Zeolite. A. 5,600 1,500 60 15 Example 77. Alumina 5, 600 l, 500 690 550 Example 78 Magnesia..- 600 1, 500 1,200 620 Control 5 Active carbou 5 600 1 2,100 1,000

wherein R is an aromatic group or a group having a terminal CH= or CH,- radical, and M is hydrogen or an alkali metal;

2. thiazole compounds of the-formula wherein R is an aromatic group and M is hydrogen or an alkali metal;

3. di-alkyldithiocarbamic acids of the formula wherein R is a C C alkyl radical and M is hydrogen or an alkali metal; and

4. xanthates of the formula ROCS-M wherein R is butyl or isopropyl and M is hydrogen or an alkali metal;

b. an organic compound capable of forming a mercaptide compound of a metal selected from: 1. thiocarbazones of the formula wherein R is an aromatic group;

2. thioureas of the formula wherein R and R are each an aromatic group or a C C alkyl radical;

3. Z-Mercaptobenzimidazole; and

4. l-Mercaptoimidazoline; and

(c) an organic compound capable of forming a chelate compound of a metal selected from anthranylic acid, oxine and Z-methyl oxine.

2. The process according to claim 1 wherein said carrier material is selected from the group consisting of carbon, silica gel, silica-alumina gel containing at least 50 percent by weight of silica gel, and zeolite.

3. The process of claim 1 wherein said metalcontaining material from which the metal is to be removed by treatment is one containing a metal or metals selected from the group consisting of Hg, Au, Bi, Cd,

5 Co, Cr, Cu, Ni, Pb, Zn, Ag, Mn, Fe, Mo, Ti, Mg and Al.

4. A treatment process for removing metals which comprises contacting a liquid phase metal-containing material from which the metal is to be removed, with a solid treating agent consisting of a carrier material and a compound deposited thereon by adsorption, said compound being selected from the group consisting of a. an organic compound capable of forming a mercaptide compound of a metal selected from 1. mercaptide compounds of the formula RSM wherein R is an aromatic group or a group having a terminal CH= or --CH, radical, and M is hydrogen or an alkali metal;

2. thiazole compounds of the formula wherein R is an aromatic group and M is hydrogen or an alkali metal;

3. di-alkyldithiocarbamic acids of the formula N=' SM R I wherein R is a C C alkyl radical and M is hydrogen or an alkali metal; and

4. xanthates of the formula RO-C-SM wherein R is butyl or isopropyl and M is hydrogen or an alkali metal; b. an organic compound capable of forming a mercaptide compound of a metal selected from 1. thiocarbazones of the formula 21 22 wherein R is an aromatic group; 5. The process of claim 4 wherein said metal- 2. thioureas of the formula containing material from which the metal is to be removed by treatment has been pre-treated with an anion R NI I exchange resin.

5 l 6. The process according to claim 4 wherein said car- R'NH rier material is selected from the group consisting of carbon, silica gel, silica-alumina gel containing at least wherein R and R are each an aromatic group or a C 50 percent by weight of silica gel, and zeolite. C alkyl radical; 7. The process of claim 4 wherein said metal- 3. Z-Mercaptobenzimidazole; and containing material from which the metal is to be re- 4. Z-Mercaptoimidazoline; and moved by treatment is one containing a metal or metals 0. an organic compound capable of forming a chelate selected from the group consisting of Hg, Au, Bi, Cd, compound of a metal selected from anthranylic Co, Cr, Cu, Ni, Pb, Zn, Ag, Mn, Fe, M0, Ti, M d AL acid, oxine and Z-methyl oxine. t

3 UNITED STATES P 'IENT ()F IeE f CERTWICATE 9F CORRECTION Patent No. 3 5 5 6 t Dated August 278', 1973 ].nventor(S)NOriVL1ki YOKOTA. Shir ITQ and Hiroshi 'TAKA'IOMI l It 'is certified that error appears in the aboveeiden'tified 'patent and that said Letters Patent are hereby ,correeted. as shown below:

Inthe Claims, column 20, line l3: delete "4. 'l- Merca tOimidazoline; and" and insert -4. Z-Mercaptoimidazoline; and-- Signed and. sealed this 25th day bfv December 1973.

(SEAL) s v e v.

EDWARD M. FLETCHERJR. i D. TEGTMEYER Atte'sting Officer 12 t Acting Commissioner of Patents 'o:-.o- I k ""uscoMw'ocooam-psg Q U 3. GOVERNMENT MUN'UNG QFFICE I969 0*366-334 

2. thioureas of the formula
 2. thiazole compounds of the formula
 2. The process according to claim 1 wherein said carrier material is selected from the group consisting of carbon, silica gel, silica-alumina gel containing at least 50 percent by weight of silica gel, and zeolite.
 2. thioureas of the formula
 2. thiazole compounds of the formula
 3. The process of claim 1 wherein said metal-containing material from which the metal is to be removed by treatment is one containing a metal or metals selected from the group consisting of Hg, Au, Bi, Cd, Co, Cr, Cu, Ni, Pb, Zn, Ag, Mn, Fe, Mo, Ti, Mg and Al.
 3. 2-Mercaptobenzimidazole; and
 3. di-alkyldithiocarbamic acids of the formula
 3. 2-Mercaptobenzimidazole; and
 3. di-alkyldithIocarbamic acids of the formula
 4. 2-Mercaptoimidazoline; and c. an organic compound capable of forming a chelate compound of a metal selected from anthranylic acid, oxine and 2-methyl oxine.
 4. xanthates of the formula R-O-C-S-M wherein R is butyl or isopropyl and M is hydrogen or an alkali metal; b. an organic compound capable of forming a mercaptide compound of a metal selected from
 4. A treatment process for removing metals which comprises contacting a liquid phase metal-containing material from which the metal is to be removed, with a solid treating agent consisting of a carrier material and a compound deposited thereon by adsorption, said compound being selected from the group consisting of a. an organic compound capable of forming a mercaptide compound of a metal selected from
 4. 1-Mercaptoimidazoline; and (c) an organic compound capable of forming a chelate compound of a metal selected from anthranylic acid, oxine and 2-methyl oxine.
 4. xanthates of the formula R-O-C-S-M wherein R is butyl or isopropyl and M is hydrogen or an alkali metal; b. an organic compound capable of forming a mercaptide compound of a metal selected from:
 5. The process of claim 4 wherein said metal-containing material from which the metal is to be removed by treatment has been pre-treated with an anion exchange resin.
 6. The process according to claim 4 wherein said carrier material is selected from the group consisting of carbon, silica gel, silica-alumina gel containing at least 50 percent by weight of silica gel, and zeolite.
 7. The process of claim 4 wherein said metal-containing material from which the metal is to be removed by treatment is one containing a metal or metals selected from the group consisting of Hg, Au, Bi, Cd, Co, Cr, Cu, Ni, Pb, Zn, Ag, Mn, Fe, Mo, Ti, Mg and Al. 